Thermoplastic article having a decorative material embedded therein

ABSTRACT

This invention relates to thermoplastic article having one or more decorative materials embedded therein which is obtained by applying heat and pressure to one or more laminates wherein at least one of said laminates comprises, in order, (1) an upper sheet material; (2) one or more decorative materials; and (3) a lower sheet material; wherein the upper and lower sheet materials are formed from a polyester/aromatic polycarbonate blend.

FIELD OF THE INVENTION

This invention pertains to a novel thermoplastic article havingdecorative materials embedded therein. More specifically, this inventionpertains to an article produced by applying heat and pressure to alaminate comprising, in order: an upper sheet material, at least onedecorative material, for example, a fabric, metallic wire, paper, orprinted layer, and a lower sheet material to produce a thermoplasticarticle having the decorative materials embedded therein. The novelthermoplastic articles provided by the present invention may be used inthe construction industry as glazing for windows, in partitions and asdecorative panels. One or both surfaces of the articles may be texturedduring or after formation of the articles.

BACKGROUND OF THE INVENTION

Glass, both transparent and translucent, has been used as glazingmaterial for windows and partitions and, for certain uses, it is paintedor stained to provide specific decorative effects. Glass is high indensity and weight, is difficult to fabricate at the work site, isgenerally brittle, and can constitute a safety hazard.

Glass substitutes such as polyvinyl chloride sheeting, acrylic, e.g.,poly(methyl methacrylate), sheeting and polycarbonate sheeting have beenused as substitutes for glass in certain glazing applications.Generally, these substitutes are made for clear (transparent),non-decorative applications. The sheet material provided by thisinvention may be used primarily for producing or obtaining decorativeapplications with varying degrees of transparency and various levels ofenhanced security.

Articles made from copolyester sheet are described in U.S. Pat. Nos.5,894,04, 5,958,539, 5,998,028, 5,643,666, and 6,025,069. However,applications exist whereby higher creep/thermal resistances compared toneat copolyester are needed, for instance backlit paneling. In addition,replacing neat copolyester with neat polycarbonate is undesirable aswell, since polycarbonate has to be dried prior to composite fabricationthereby increasing cycle time and cost. Polycarbonate also must belaminated at high temperatures, which can cause degradation of thedecorative layer. Further, polycarbonate is difficult to post-formwithout pre-drying and requires higher forming temperatures.

U.S. Pat. No. 5,413,870 describes a sturdy wall covering especiallyuseful in a bathroom or shower area, the wall covering being comprisedof a laminate that includes a clear or transparent acrylic cast in thefirst layer, a clear polyester thermoset resin in the second layer, anda thin fabric sheet as the third layer and a pigmented polyesterthermoset coating over the fabric layer. The polyester thermosettingresins in this case are applied as a liquid and subsequently cured as asolid. There are several difficulties when using polyester thermosettingresins. Removing air bubbles from the liquid thermosetting resins can bedifficult. Thermosetting resins can undergo significant shrinkage duringcuring. In addition, crosslinked polyester resins are known to bebrittle. This invention alleviates many of these difficulties.

Advantages of this invention over the prior art include higher heatdeflection temperature (HDT), increased stiffness and increased creepresistance with time.

SUMMARY OF THE INVENTION

The present invention provides a thermoplastic article, typically in theform of sheet material, having a decorative material embedded therein.The thermoplastic article is obtained by applying heat and pressure toone or more laminates or “sandwiches”, wherein at least one of saidlaminates comprises, in order, (1) at least one upper sheet material,(2) at least one decorative material, and (3) at least one lower sheetmaterial. Optionally, an adhesive layer may be used between (1) and (2)and/or between (2) and (3).

The upper and lower sheet materials are produced from misciblepolyester/polycarbonate blends. The polyester component, as describedbelow, preferably comprises a minimum level of 1,4 cyclohexanedimethanolas a comonomer in order to effect miscibility with polycarbonate.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a thermoplastic article having a decorativematerial embedded therein obtained by applying heat and pressure to oneor more laminates wherein at least one of said laminates comprises, inorder, (1) at least one upper sheet material, (2) at least onedecorative material comprising metallic wire, rods or bars; naturalfibers; glass fibers, mineral fibers, fabric, paper, and/or printedlayer; and (3) at least one lower sheet material; wherein the upper andlower sheet materials are formed from a miscible polyester/aromaticpolycarbonate blend comprising:

-   (a) 1 to 99 weight % of a polyester, comprising a diacid residue    component selected from the group consisting of aliphatic,    alicyclic, and/or aromatic dicarboxylic acids, wherein the aromatic    portion of said aromatic dicarboxylic acid has 6–20 carbon atoms,    wherein the aliphatic or alicyclic portion of said aliphatic or    alicyclic dicarboxylic acid has 3–20 carbon atoms, and a glycol    residue component comprising from 45 mole % to 100 mole %    1,4-cyclohexanedimethanol, and, optionally, at least one additional    aliphatic glycol having 2–20 carbon atoms; wherein the total mole    percentages for the glycol component equals 100 mole %.-   (b) 99 to 1 weight % of an aromatic polycarbonate; wherein the total    combined weight percentage of polyester and polycarbonate in the    polyester/polycarbonate blend equals 100 weight %.

A preferred blend composition is 50–90 weight % by weight of thepolyester and 50–10 weight % by weight of the aromatic polycarbonate. Aneven more preferred composition is 60–80 weight % polyester and 40–20weight % by weight aromatic polycarbonate.

Polyesters suitable in the context of the present invention arepolyesters having repeating unit of the Formula I:

wherein R is the residue of 1,4 cyclohexanedimethanol or a mixture of1,4 cyclohexanedimethanol and at least one aryl, alkane or cycloalkanecontaining diol having 2 to 20 carbon atoms or chemical equivalentthereof; and wherein R₁ is the decarboxylated residue derived from anaryl, aliphatic, or cycloalkane containing diacid of 3 to 20 carbonatoms or chemical equivalent thereof. Examples of the diol portion, R,are ethylene glycol, 1,2-propylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2- or1,3-cyclohexanedimethanol, neopentyl glycol, and 2,2,4,4tetramethyl-1,3-cyclobutanediol. The preferred second glycol is ethyleneglycol. Examples of the diacid portion, R¹, are malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic,1,4-, 1,5-, and 2,6-decahydronaphthalenedicarboxylic acid, and cis- ortrans-1,4-cyclohexanedicarboxylic acid. Examples of useful aromaticdicarboxylic acids are terephthalic acid, isophthalic acid,4,4′-biphenyldicarboxylic, trans 3,3′- and trans 4,4stilbenedicarboxylic acid, 4,4′-dibenzyldicarboxylic acid, 1,4-, 1,5′-,2,3-, 2,6, and 2,7-naphthalenedicarboxylic acid. Chemical equivalents ofthese diacids include esters, alkyl esters, dialkyl esters, diarylesters, anhydrides, salts, acid chlorides, acid bromides, and the likeand are included within the scope of this invention. The preferreddicarboxylic acids are terephthalic and isophthalic acid or mixturesthereof. The preferred chemical equivalent comprises dialkyl esters ofterephthalic and isophthalic acid. Mixtures of any of these acids orequivalents can be used.

A preferred polyester useful within the scope of this invention is apolyester having from 40 to 100 mole %, more preferably 60 to 80 mole %of 1,4-cyclohexanedimethanol wherein the total mole percentages of theglycol component in the polyester equal 100 mole %. The remainder of theglycol component may be any of the other glycols described herein butpreferably is ethylene glycol in the amount of 0 to 60 mole %, morepreferably, 20 to 40 mole %. Although any diacid as described herein maybe used, 80 to 100 mole % terephthalic acid, is preferred for thisembodiment.

Another preferred polyester useful within the scope of this invention isa polyester having from 100 mole % 1,4-cyclohexanedimethanol wherein thetotal mole percentages of the glycol component in the polyester equal100 mole %. Also, in this particular embodiment, it is preferred thatisophthalic acid is present in the amount of 5 to 50 mole %, morepreferably, 20 to 40 mole %. Although any diacid as described herein maybe used, it is preferred that terephthalic acid is present in the amountof 95 to 50 mole %.

Conventional polycondensation processes, well known in the art, are usedto prepare the polyesters of the present invention. These include directcondensation of the acid(s) with the diol(s) or by ester interchangeusing lower alkyl esters. The inherent viscosity of the polyesters ofthe present invention may range from about 0.4 to 1.0 dl/g at 25° C. ina solvent consisting of 60% by weight phenol and 40% by weighttetrachlorethane.

The polymerization reaction may be carried out in the presence of one ormore conventional polymerization catalysts. Typical catalysts orcatalyst systems for polyester condensation are well known in the art.Suitable catalysts are disclosed, for example, in U.S. Pat. Nos.4,025,492, 4,136,089, 4,176,224, 4,238,593, and 4,208,527, thedisclosures of which are herein incorporated by reference. Further, R.E. Wilfong, Journal of Polymer Science, 54, 385, (1961) describestypical catalysts, which are useful in polyester condensation reactions.Preferred catalyst systems include Ti, Ti/P, Mn/Ti/Co/P, Mn/Ti/P,Zn/Ti/Co/P, Zn/Al, and Li/Al. When cobalt is not used in thepolycondensation, copolymerizable toners may be incorporated into thecopolyesters to control the color of these copolyesters so that they aresuitable for the intended applications where color may be an importantproperty. In addition to the catalysts and toners, other conventionaladditives, such as antioxidants, dyes, etc., may be used in thecopolyesterifications in typical amounts.

One or more branching agents may also be useful in making the polyestersformed within the context of the invention. The branching agent can beone which provides branching in the acid unit portion of the polyester,or in the glycol unit portion, or it can be a hybrid. Some of thesebranching agents have already been described herein. However,illustrative of such branching agents are polyfunctional acids,polyfunctional glycols and acid/glycol hybrids. Examples include tri ortetracarboxylic acids, such as trimesic acid, pyromellitic acid andlower alkyl esters thereof and the like, and tetrols such aspentaerythritol. Also triols such as trimethylopropane or dihydroxycarboxylic acids and hydroxydicarboxylic acids and derivatives, such asdimethyl hydroxy terephthalate, and the like are useful within thecontext of this invention. Trimellitic anhydride is a preferredbranching agent. The branching agents may be used either to branch thepolyester itself or to branch the polyester/polycarbonate blend of theinvention.

Polycarbonates useful in this invention comprise the divalent residue ofdihydric phenols bonded through a carbonate linkage and are representedby structural formulae II and III.

wherein:A denotes an alkylene group with 1 to 8 carbon atoms; an alkylidenegroup with 2 to 8 carbon atoms; a cycloalkylene group with 5 to 15carbon atoms; a cycloalkylidene group with 5 to 15 carbon atoms; acarbonyl group; an oxygen atom; a sulfur atom; —SO— or —SO₂; or aradical conforming to e and g both denote the number 0 to 1; Z denotesF, Cl, Br or C₁₋₄.alkyl; and if several Z radicals are substituents inone aryl radical, they may be identical or different from one another; ddenotes an integer of from 0 to 4; and f denotes an integer of from 0 to3.

By the term “alkylene” is meant a bivalent saturated aliphatic radicalwherein the two valences are on different carbon atoms, e.g., ethylene,;1,3-propylene; 1,2-propylene; 1,4-butylene; 1,3-butylene; 1,2- butylene,amylene, isoamylene, etc. By the term “alkylidene” is meant a bivalentradical wherein the two valences are on the same carbon atoms, e.g.,ethylidene, propylidene, isopropylidine, butylidene, isobutylidene,amylidene, isoamylidene, 3,5,5,-trimethylhexylidene. Examples of“cycloalkylene” are cyclopropylene, cyclobutylene, and cyclohexylene.Examples of “cycloalkylidene” are cyclopropylidene, cyclobutylidene, andcyclohexylidene. Examples of C₁₋₄.alkyl are methyl, ethyl, propyl,isopropyl, butyl, and isobutyl.

The dihydric phenols employed are known, and the reactive groups arethought to be the phenolic hydroxyl groups. Typical of some of thedihydric phenols employed are bis-phenols such as2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A),3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)-cyclohexane,2,4-bis-(4-hydroxyphenyl)-2-methyl-butane,1,1-bis-(4-hydroxyphenyl)-cyclohexane, alpha,alpha′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene,2,2-bis-(3-methyl4-hydroxyphenyl)propane,2,2-bis-(3-chloro-4-hydroxyphenyl)propane,bis-(3,5-dimethyl4-hydroxyphenyl)-methane,2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane,bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfide,bis-(3,5dimethyl-4-hydroxyphenyl)-sulfoxide,bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, dihydroxy-benzophenone,2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane,alpha.,.alpha.′-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzeneand 4,4′-sulfonyl diphenol. Other dihydric phenols might includehydroquinone, resorcinol, bis-(hydroxyphenyl)-alkanes,bis(hydroxyphenyl)ethers, bis-(hydroxyphenyl)-ketones,bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-sulfides,bis-(hydroxyphenyl)-sulfones, and .alpha.,.alpha.-bis-(hydroxyphenyl)diisopropylbenzenes, as well as theirnuclear-alkylated compounds. These and further suitable dihydric phenolsare described, for example, in U.S. Pat. Nos. 2,991,273; 2,999,835;2,999,846; 3,028,365; 3,148,172; 3,153,008; 3,271,367; 4,982,014;5,010,162 all incorporated herein by reference. The polycarbonates ofthe invention may entail in their structure, units derived from one ormore of the suitable bisphenols. The most preferred dihydric phenol is2,2-bis-(4hydroxyphenyl)-propane (bisphenol A).

The carbonate precursors are typically a carbonyl halide, adiarylcarbonate, or a bishaloformate. The carbonyl halides include, forexample, carbonyl bromide, carbonyl chloride, and mixtures thereof. Thebishaloformates include the bishaloformates of dihydric phenols such asbischloroformates of 2,2-bis(4-hydroxyphenyl)-propane, hydroquinone, andthe like, or bishaloformates of glycol, and the like. While all of theabove carbonate precursors are useful, carbonyl chloride, also known asphosgene, and diphenyl carbonate are preferred.

The aromatic polycarbonates can be manufactured by any processes such asby reacting a dihydric phenol with a carbonate precursor, such asphosgene, a haloformate or carbonate ester in melt or solution. Suitableprocesses are disclosed in U.S. Pat. Nos. 2,991,273; 2,999,846;3,028,365; 3,153,008; 4,123,436; all of which are incorporated herein byreference.

The polycarbonates of this invention have a weight average molecularweight, as determined by gel permeation chromatography, of about 10,000to 200,000, preferably 15,000 to 80,000 and their melt flow index, perASTM D-1238 at 300° C. is about 1 to 65 g/10 min, preferably about 2 to30 g/10 min. The polycarbonates may be branched or unbranched. It iscontemplated that the polycarbonate may have various known end groups.These resins are known and are readily available in commerce.

One or more branching agents may also be used in making thepolycarbonates of the invention. Branching agents, such as tri- andtetrafunctional phenols and carbonic acids, as well as bisphenols withcarbonic acid side chains are typically used. An example might include1,4-bis(4′,4″-dihydroxytriphenylmethyl)benzene, and trisphenol TC.Nitrogen-containing branching agents are also used. Examples mightinclude: cyanic chlorid and3,3-bis(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

Polymer miscibillity is defined herein as a polymer forming a singlephase.

The preferred miscible blends of this invention were first disclosed inResearch Disclosure 22921, May, 1983, which concerns blends ofpolycarbonate with polyesters based on terephthalic acid and a mixtureof 1,4-cyclohexanedimethanol and ethylene glycol. Similar miscibleblends are disclosed in U.S. Pat. Nos. 4,786,692 and 5,478,896. Blendsof polycarbonate with another family of polyesters, those based on amixture of terephthalic and isophthalic acids with1,4-cyclohexanedimethanol, are disclosed in U.S. Pat. Nos. 4,188,314 and4,391,954. British Patent Specification 1,599,230 (published Jan. 16,1980) discloses blends of polycarbonate with polyesters of1,4-cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid. Mohnet al. reported on thermal properties of blends of polyesters based on1,4-cyclohexanedimethanol and terephthalic acid orterephthalic/isophthalic acid mixtures with polycarbonate [J. Appl.Polym. Sci., 23, 575 (1979)], concluding that there were only slightdifferences in behavior between the two systems, and that these resultswere not unexpected. More recently, improvement to these miscible blendsystems have been achieved and filed by the writers.

While a preferred embodiment of the invention is the “sandwich”embodiment described herein consisting of upper sheet material (1),decorative layer (2) and lower sheet material (3), it is also within thescope of this invention that multiple “sandwiches” can be present withthe “sandwiches” simply being replicated. It is further within the scopeof this invention that the multiple “sandwiches” embodiment shares onelayer in common, namely, layers (1) or (3), i.e., such as a laminateconsisting of the following layers, in order: sheet material, decorativelayer, sheet material, decorative layer, sheet material, etc.

Optionally, an adhesive layer may be used between the upper sheetmaterial (1) and the decorative layer (2) and/or between the lower sheetmaterial (3) and the decorative layer (2). In the multilaminateembodiments, an adhesive layer can also be applied between laminates.The adhesive layer can comprise any adhesive known in the art. Specificexamples within the scope of this invention are polyurethane, modifiedpolyethylenes, sulfopolyesters, epoxy coatings all of which are known inthe art. Sulfopolyesters useful as adhesives in the practice of thisinvention can be either linear or branched. Preferred sulfopolyestershave a glass transition temperature (denoted as Tg) between −25° C. and+90° C. More preferred sulfopolyesters have a Tg between 0° C. and +65°C. Even more preferred sulfopolyesters have a Tg between +5° C. and +55°C. Useful sulfopolyesters and their methods of preparation are describedin U.S Pat. Nos. 3,546,008; 3,734,874; 4,233,196; 4,946,932; 5,543,488;5,552,495; 5,290,631; 5,646,237; 5,709,940; and 6,162,890.Alternatively, water dispersible phosphopolyesters, such as thosedescribed in U.S. Pat. No. 4,111,846 can be used advantageously butthese polymers suffer from a lack of hydrolytic stability in aqueoussystems and are, therefore, less desirable for practical use.

In addition to the preferred Tg ranges delineated above, usefulsulfopolyesters have an inherent viscosity (a measure of molecularweight) of a least 0.1 and preferably at least 0.2 and more preferablyat least 0.3 as measured in a 60/40 parts by weight solution ofphenol/tetrachloroethane at 25° C. and a concentration of about 0.25grams of polymer in 100 mL of solvent. For branched sulfopolyesters,such as those described in U.S. Pat. No. 5,543,488, preferredcompositions have a number-average-molecular weight (Mn) of at least4000 daltons.

The polyester/polycarbonate blends of this invention maybe made byconventional melt processing techniques. For examples, pellets of thepolyester may be mixed with pellets of the polycarbonate andsubsequently melt blended on either a single or twin screw extruder toform a homogenous mixture.

The miscible blend compositions of the invention may contain impactmodifiers, UV stabilizers, stabilizers, nucleating agents, extenders,flame retarding agents, reinforcing agents, fillers, antistatic agents,mold release agents, colorants, antioxidants, extrusion aids, slipagents, release agents, carbon black, and other pigments, and the likeall and mixtures thereof which are known in the art for their utility inpolyester/polycarbonate blends. In particular, the use of phosphorousbased stabilizers for further color reductions, if needed, is well knownin the art.

The second component of the thermoplastic articles of the presentinvention comprises a decorative material. The decorative material maycomprise metallic wire, rods or bars; natural fibers, glass fibers,mineral fibers, fabric, papers; and printed layers.

For instance, fabric may be used as a decorative material to beencapsulated. The fabric may display images or decorative designs thathave been produced, e.g., by weaving or knitting techniques, in thefabric. The fabrics, which may be used in producing the articles of thepresent invention, comprise textile fibers, i.e., fibers ofnatural-occurring, semisynthetic or synthetic polymeric materials. Forexample, the fabrics may be prepared from cotton, wool, silk, rayon(regenerated cellulose), polyester such as poly(ethylene terephthalate),synthetic polyamides such as nylon 66 and nylon 6, synthetic polyolefinssuch as polyethylene and polypropylene, acrylic, modacrylic andcellulose acetate fibers. The melting point of the textile fibers shouldbe sufficiently high to avoid any degradation or distortion of thefabric during the manufacture or processing of the articles of thisinvention. The fabric may be woven, spun-bonded, knitted, or prepared byother processes well known in the textile trade and may be uncolored,e.g., white, or colored by conventional dyeing and printing techniques.Alternatively, the fabrics may be produced from dyed yarn or fromfilaments and yarn derived from mass colored polymers. Normally, thefabrics present within the thermoplastic articles of the presentinvention are substantially continuous and constitute a distinct layer.One embodiment of our invention, therefore, is a novel laminate articlecomprising, in order, (1) a layer of a miscible polyester/polycarbonateblend, (2) a fabric layer composed or made of textile fibers, and (3) asecond layer of a miscible polyester/polycarbonate blend as describedhereinabove.

As another example, the second component (decorative component) of thethermoplastic articles of the present invention may comprise metallicwire, rod or bar. The metal wire may be formed by a variety oftechniques to produce metal mesh fabric, screens, or open mesh havinghigh transparency. The metal wire, rod or bar may be woven, welded,knitted, or fabricated by means of other processes well known in themetal wire fabrication trade. The metallic wire, rod and bar may be ofvarious colors such as black, gray, green, blue, etc. The metallicelement can be composed of different metallic materials such copper,aluminum, stainless steel, steel, galvanized steel, titanium, etc. orcombinations thereof. The metallic component of the thermoplasticarticles may be prepared from wire filaments, rods and bars havingvarious cross-sectional areas and geometries, e.g., generally circular,oval or relatively flat. The thickness or diameter of the wire, rod andbar may range from about 0.001 to 19 mm (0.00004 to 0.75 inch) dependingupon the end use of the thermoplastic article. However, for most of thearticles of the present invention the thickness or diameter the wire,rod and bar will be in the range of about 0.0254 to 5.08 mm (0.001 to0.20 inch). One embodiment of our invention, therefore, is a novellaminate article comprising, in order, (1) a layer of a misciblepolyester/polycarbonate blend, (2) a metal wire mesh, and (3) a secondlayer of a miscible polyester/polycarbonate blend is describedhereinabove.

Still further, the decorative component may be decorative or printedpapers, colored films, films printed with an image or picture, and thelike.

The thermoplastic articles of our invention can be used in themanufacture of decorative walls, partitions, and glazing applications.The thermoplastic articles are thermoformable according to methods knownin the art of thermoforming.

The upper and lower sheet materials used in the manufacture of thethermoplastic articles of the present invention may be the same ordifferent. For example, the upper and lower sheet materials may beproduced from different miscible polyester/polycarbonate blends (asdefined herein) or miscible compositions that contain differentadditives, e.g., pigment additives that alter the transparency of themiscible polyester/polycarbonate sheeting.

The sheet material used in the preparation of the thermoplastic articlesof our invention may be transparent, translucent, or one layer may beopaque, depending on the particular aesthetic effect desired. The upperand lower sheet materials may differ in degree of transparency ortranslucency and also in color. When the upper and lower sheet materialsare produced from different miscible polyester/polycarbonate blends, themiscible polyester/polycarbonate blends must be thermally compatible. Asused herein, the term “thermal compatibility” means that when layers ofthe sheet materials are bonded together under conditions of elevatedtemperature and pressure, the layers undergo approximately equal thermalexpansion or contraction such that the solid surface is substantiallyplanar.

The thickness of the sheet materials used in the preparation of thethermoplastic articles is not an important feature of the presentinvention and depends upon a number of factors such as functionality,weight, cost and the like. The sheet material from which the upper (orouter) layer or surface is formed generally has a thickness in the rangeof about 0.76 to 6.4 mm (0.03–0.25 inch), preferably in the range ofabout 1.6 to 3.2 mm (0.063–0.126 inch). The sheet material from whichthe lower (or backing) layer or surface is formed typically has athickness in the range of about 0.76 to 6.4 mm (0.03–0.25 inch),preferably about 3.2 mm (0.126 inch).

The thermoplastic article of the present invention may be produced bysubjecting the laminate to temperatures and pressures sufficient tocause the upper and lower sheet materials to bond (or fuse) to eachother. However, temperatures which cause decomposition, distortion, orother undesirable effects in the finished article or sheet material,should be avoided. Avoidance of such extreme temperatures is anadvantage of the miscible polyester/polycarbonate sheet materials of thepresent invention compared to the use of neat polycarbonate sheet.Normally, the bonding temperatures are in the range of about 90 to 300°C. (194 to 572° F.), preferably in the range of about 129 to 260° C.(265 to 500° F.). The pressures utilized in the bonding or laminating ofthe sandwich preferably are in the range of about 0.65 to 3.45 MPa(about 95 to 500 pounds per square inch—psi). The optimal temperaturefor bonding the thermoplastic articles will vary depending, for example,on the particular miscible copolyester/polycarbonate blend employed andthe thickness of the sheet materials used, and may be determined bythose skilled in the art. The sandwich or laminate is held at theappropriate temperature and pressure for about 4 to 24 minutes, or untilsuch time as a bond is formed between the upper and lower sheetmaterials. After 4 to 24 minutes, the bonded/fused thermoplastic articleis allowed to cool under pressures from about 0.69 to 2.4 MPa (about 100to 350 psi), preferably about 1.4 MPa (200 psi), until it cools belowthe glass transition temperature of the miscible polyester/polycarbonateblend sheet material(s). During the bonding process, the misciblepolyester/polycarbonate blend sheet materials may be bonded or fused toeach other without the use of an adhesive. The lamination process mayutilize adhesives or coupling agents on the fabric to enhance theadhesion of the thermoplastic sheet materials to the decorativematerial.

The miscible polyester/polycarbonate blends constituting the sheetmaterials used in the manufacture of the articles and sheeting of thepresent invention may not be as hard or scratch resistant as may benecessary or desired for certain end uses. For example, an end use inwhich the exterior surface of the thermoplastic article may be subjectedto scratching or abrasion, i.e., in a privacy partition, may require theapplication of an abrasion-resistant coating to one or both of theexterior surfaces. For example, films consisting of fluorinatedhydrocarbons, poly(perfluoroethylene) such as TEDLAR from duPontChemical Company or oriented poly(ethylene terephthalate) such as MYLARfrom duPont Chemical Company may be used to improve both chemical andabrasion resistance. The abrasion resistant film typically has athickness in the range of about 0.025 to 0.254 mm (0.001–0.01 inch),preferably about 0.051 to 0.178 mm (0.002–0.007 inch), and mostpreferably about 0.076 mm (0.003 inch). However, abrasion resistant filmthinner or thicker than these ranges may be used since the thickness ofsuch film is limited only by the equipment available cost andfunctionality considerations. An adhesive optionally may be used betweenthe miscible copolyester/polycarbonate blend and the abrasion resistantfilm.

Alternatively, an abrasion resistant coating may be applied to a plasticfilm and then the film bearing the abrasion resistant coating may belaminated to one or both sides of the article or sheeting of the presentinvention. The film may be selected from a number of thermoplasticmaterials compatible with the lamination process such as poly(vinylchloride), PETG copolyester, poly(ethylene terephthalate), poly(methylmethacrylate), polycarbonate, miscible polyester/polycarbonate blends,and the like. PETG is defined herein as a polyester comprising,terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol.Preferably, PETG comprises from 80 to 100 mole % terephthalic acid, 20to 60 mole % 1,4-cyclohexanedimethanol and 80 to 40 mole % ethyleneglycol based on the mole percentages for diacids totaling 100 mole % andthe mole percentages for diols totaling 100 mole %.

The film thickness may range from 0.0025–0.381 mm (0.001–0.015 inch)with a thickness of 0.0762–0.203 mm (0.003–0.008) being most preferred.The coating may be selected from a number of commercially-availablematerials such as polyurethanes, fluorinated polyurethanes and siliconeswhich are cured by heat or they may be selected from materials that arecured by ultraviolet (UV) or electron beam (EB) radiation. Such UV/EBcured materials fall under the general class of acrylates and modifiedacrylates that contain fluorine, silicone, epoxy, polyester, polyetheror caprolactone residues or functional groups. The particular coatingmaterial selected will depend primarily on the degree of abrasionresistance required. Application of the liquid, heat- or UV/EB-curableprecursor of the abrasion resistant coating may be carried out accordingto conventional procedures and usually is accomplished on a roll coatingmachine. The thickness of the coating applied to a film generally is0.0076–0.051 mm (0.0003–0.002 inch) with thickness of about 0.0127 mm(0.0005 inch) being most preferred.

These coatings may be applied in a manner similar to the application ofpaints. The coatings exist either as predominantly undiluted materialwith very little volatile content or as solvent- or water-basedmaterials. In addition to being applied to a film that can be laminatedto the structure as part of the process, they may be applied directly tothe finished product. Application may be carried out by a variety oftechniques such as roll, paint, spray, mist, dip and the like.

The thermoplastic article or laminate, based on the misciblepolyester/polycarbonate blend, can be subsequently shaped andthermoformed into a variety of useful products. As an illustrativeexample, the thermoplastic article can be thermoformed or otherwiseshaped into sliding glass doors, shower doors, entrance doors, privacypartitions, multi-paned windows, and tabletops and other furniturepieces. Depending on the nature of the decorative material, thethermoplastic articles of this invention may be formed, heat draped, ormolded. In addition, the articles of the present invention have anappealing appearance with low density to facilitate transport andinstallation of building materials produced there from.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated. The starting materials are commerciallyavailable unless otherwise indicated.

EXAMPLES Example 1

Two decorative laminates were prepared for this example. Laminate A wascomprised of a polyethylene based fabric sandwiched in between two ⅛″sheets of a miscible copolyester/polycarbonate blend (75 wt % PCTG/25 wt% PC). The total laminate thickness was ¼″. Laminate B was comprised ofa polyethylene based fabric sandwiched in between two ⅛″ sheets of aneat copolyester (PETG). The two laminate sheets, which measured 2′×2′,were then placed in a clamped frame and subjected to a uniform load (10psi) at 60 C. After 10 hours, the center (maximum) deflection of the twolaminates, still under load, was measured. Laminate A had a deflectionof 3.5″, while laminate B had a deflection of 4.5″. This exampleillustrates the advantages of laminate A compared to laminate B. PETG inthis example is poly(ethylene terephthalate) modified with 31 mole %1,4-cyclohexanedimethanol. PCTG in this example ispoly(cyclohexylenedimethylene terephthalate) modified with 34 mole %ethylene glycol. PC in this example refers to polycarbonate, namely,bisphenol A.

Example 2

Two decorative laminates were prepared for this example. Laminate A wascomprised of a polyethylene based fabric sandwiched in between two ⅛″sheets of a miscible copolyester/polycarbonate blend (75 wt % PCTG/25 wt% PC). The total laminate thickness was ¼″. Laminate B was comprised ofa polyethylene based fabric sandwiched in between two ⅛″ sheets of aneat (PC). The two laminate sheets, A and B, prepared measured 2′×2′.The two laminates were allowed to equilibrate to the lab environment, inparticular moisture level, for two months. After equal equilibration,the two laminates were placed into a Brown thermoforming unit to form ashaped article, in this case a cup. The formed article from laminate Bshowed severe blistering. The formed article from laminate A showed noblistering. This example illustrates the advantages of laminate Acompared to laminate B. PCTG in this example ispoly(cyclohexylenedimethylene terephthalate) modified with 34 mole %ethylene glycol. PC in this example is polycarbonate, namely, bisphenolA.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1. A thermoplastic article having one or more decorative materialsembedded therein obtained by applying heat and pressure to one or morelaminates wherein at least one of said laminates comprises, in order,(1) an upper sheet material; (2) one or more decorative materials; and(3) a lower sheet material; wherein the upper and lower sheet materialsare formed from a polyester/aromatic polycarbonate blend, comprising:(a) 1 to 99 weight % of a polyester comprising a diacid residuecomponent selected from the group consisting of aliphatic or alicyclicdicarboxylic acids and/or aromatic dicarboxylic acids, wherein thearomatic portion of said aromatic dicarboxylic acid has 6–20 carbonatoms, wherein the aliphatic or alicyclic portion of said aliphatic oralicyclic dicarboxylic acid has 3–20 carbon atoms; and a glycol residuecomponent comprising from 45 mole % to 100 mole %1,4-cyclohexanedimethanol, and optionally, at least one additionalaliphatic glycol having 2–20 carbon atoms; wherein the total molepercentages for the glycol component equals 100 mole %, and (b) 99 to 1weight % of an aromatic polycarbonate; wherein the total combined weightpercentage of polyester and polycarbonate in the polyester/polycarbonateblend equals 100 weight %.
 2. The thermoplastic article of claim 1wherein the polyester/aromatic polycarbonate blend comprises saidpolyester in the amount of 50 to 90 weight % and said aromaticpolycarbonate in the amount of 50 to 10 weight %.
 3. The thermoplasticarticle of claim 2 wherein the polyester/aromatic polycarbonate blendcomprises said polyester in the amount of 60 to 80 weight % and saidaromatic polycarbonate in the amount of 40 to 20 weight %.
 4. Thethermoplastic article of claim 1 wherein the polyester in saidpolyester/aromatic polycarbonate blend comprises the formula:

wherein R is the diol residue component comprising the residue of 45 to100 mole % 1,4-cyclohexanedimethanol and 55 to 0 mole % of at least onearyl, alkane or cycloalkane containing diol having 2 to 20 carbon atomsor chemical equivalent thereof; and wherein R¹ is the diacid residuecomponent comprising the dicarboxylic acid residue derived from an aryl,aliphatic, or cycloalkane containing diacid of 3 to 20 carbon atoms orchemical equivalent thereof.
 5. The thermoplastic article of claim 4wherein said diol residue component of said polyester is selected fromthe group consisting of ethylene glycol, 1,2-propylene glycol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-or 1,3-cyclohexanedimethanol, neopentyl glycol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol.
 6. The thermoplastic article ofclaim 4 wherein said diacid residue component of said polyester isselected from the group consisting of the following acids: malonic,succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,dodecanedioic, 1,4-, 1,5-, and 2,6-decahydronaphthalenedicarboxylicacid, and cis- or trans-1,4-cyclohexanedicarboxylic acid, terephthalicacid, isophthalic acid, 4,4′-biphenyldicarboxylic, trans 3,3′- and trans4,4′-stilbenedicarboxylic, 4,4′-dibenzyldicarboxylic, and 1,4-, 1,5-,2,3-, 2,6-, and 2,7-naphthalenedicarboxylic.
 7. The thermoplasticarticle of claim 1 wherein said polyester of said polyester/aromaticpolycarbonate blends comprises terephthalic acid and1,4-cyclohexanedimethanol.
 8. The thermoplastic article of claim 7wherein said polyester of said polyester/aromatic polycarbonate blendscomprises terephthalic acid, 1,4-cyclohexanedimethanol, and ethyleneglycol.
 9. The thermoplastic article of claim 4 wherein said polyestercomprises terephthalic acid in the amount of 80 to 100 mole %,1,4-cyclohexanedimethanol in the amount of 45 to 100 mole % and ethyleneglycol in the amount of 0 to 55 mol%.
 10. The thermoplastic article ofclaim 9 wherein said polyester comprises terephthalic acid in the amountof 80 to 100 mole %, 1,4-cyclohexanedimethanol in the amount of 60 to 80mole % and ethylene glycol in the amount of 40 to 20 mole %.
 11. Thethermoplastic article of claim 1 wherein said polyester of saidpolyester/aromatic polycarbonate blends comprises terephthalic acid,isophthalic acid, and 1,4-cyclohexanedimethanol.
 12. The thermoplasticarticle of claim 11 wherein said polyester comprises terephthalic acidin the amount of 50 to 95 mole %, isophthalic acid in the amount of 5 to50 mole %, and 1,4-cyclohexanedimethanol in the amount of 90 to 100 mole%.
 13. The thermoplastic article of claim 12 wherein said polyestercomprises 1,4-cyclohexanedimethanol in the amount of 100 mole %.
 14. Thethermoplastic article of claim 1 wherein said polyester comprisesbranching agents selected from polyfunctional acids, polyfunctionalglycols and acid/glycol hybrids.
 15. The thermoplastic article of claim14 wherein said branching agents are selected from the group consistingof trimesic acid, pyromellitic acid, trimellitic anhydride, pyromelliticanhydride, trimethylopropane, dimethyl hydroxyl terephthalate, andpentaerythritol.
 16. The thermoplastic article of claim 1 wherein saidaromatic polycarbonate is produced from the reaction of one or moredihydric phenols with a carbonate precursor.
 17. The thermoplasticarticle of claim 1 wherein said dihydric phenol is selected from thegroup consisting of 2,2-bis-(4-hydroxyphenyl)-propane),3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)-cyclohexane,2,4-bis-(4-hydroxyphenyl)-2-methyl-butane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,.alpha,.alpha.′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene,2,2-bis-(3-methyl4-hydroxyphenyl)-propane,2,2-bis-(3-chloro-4-hydroxyphenyl)propane,bis-(3,5-dimethyl4-hydroxyphenyl)-methane,2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane,bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfide,bis-(3,5dimethyl-4-hydroxyphenyl)-sulfoxide,bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, dihydroxy-benzophenone,2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane,.alpha.,.alpha.′-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzeneand 4,4′-sulfonyl diphenol, hydroquinone, resorcinol,bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)ethers,bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfoxides,bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-sulfones, andalpha.,alpha.-bis-(hydroxyphenyl)diisopropylbenzenes.
 18. Thethermoplastic article of claim 17 wherein said dihydric phenol is2,2-bis-(4-hydroxyphenyl)-propane.
 19. The thermoplastic article ofclaim 16 wherein said carbonate precursor is selected from the groupconsisting of a carbonyl halide, a diarylcarbonate, and abishaloformate.
 20. The thermoplastic article of claim 19 wherein saidcarbonyl halide is selected from the group consisting of carbonylbromide, carbonyl chloride, and mixtures thereof.
 21. The thermoplasticarticle of claim 19 wherein said bishaloformates are selected from thegroup consisting of bischloroformates of2,2-bis(4-hydroxyphenyl)-propane, hydroquinone, and the like andbishaloformates of glycol.
 22. The thermoplastic article of claim 20wherein said carbonyl halide is carbonyl chloride.
 23. The thermoplasticarticle of claim 19 wherein said diarylcarbonate is diphenyl carbonate.24. The thermoplastic article of claim 1 wherein said polycarbonatecomprises one or more branching agents selected from the groupconsisting of tri- and tetrafunctional phenols, carbonic acids, andbisphenols with carbonic acid side chains.
 25. The thermoplastic articleof claim 1 wherein said polycarbonate comprises one or more branchingagents selected from 1,4-bis(4′,4″-dihydroxytriphenylmethyl)benzene, andtrisphenol TC.
 26. The thermoplastic article of claim 1 wherein saidpolycarbonate comprises nitrogen-containing branching agents.
 27. Thethermoplastic article of claim 1 wherein said polycarbonate comprisesone or more branching agents selected from the group consisting ofcyanic chloride and 3,3-bis(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.28. The thermoplastic article of claim 1 wherein said blend comprisesone or more additives selected from the group consisting of impactmodifiers, UV stabilizers, phosphorous stabilizers, nucleating agents,extenders, flame retarding agents, reinforcing agents, fillers,antistatic agents, mold release agents, colorants, antioxidants,extrusion aids, slip agents, release agents, carbon black, and otherpigments.
 29. The thermoplastic article of claim 1 wherein saiddecorative material is selected from the group consisting of selectedfrom the group consisting of metallic wire, rods or bars; naturalfibers, glass fibers, mineral fibers, fabric, papers; and printedlayers.
 30. The thermoplastic article of claim 1 wherein the upper andlower sheet materials have a thickness in the range of 0.76 to 6.4 mmand the thickness of said decorative material is in the range of 0.254to 5.08 mm.
 31. The thermoplastic article of claim 1 wherein the articleincludes an abrasion-resistant coating on one or both of the outsidesurfaces of the article.
 32. The thermoplastic article of claim 31wherein the abrasion resistant coating is provided as a film having athickness in the range of 0.0127 to 0.254 mm.
 33. The thermoplasticarticle of claim 31 wherein the abrasion resistant film is provided as afluorinated hydrocarbon, poly(perfluoroethylene), acrylic or orientedpoly(ethylene terephthalate) film having a thickness in the range of0.017 to 0.254 mm.
 34. The thermoplastic article of claim 31 wherein theabrasion resistant coating is a heat-, ultraviolet- or electronbeam-cured material on a film of poly(vinyl chloride), PETGcopolyesters, poly(ethylene terephthalate), poly(methyl methacrylate) orpolycarbonate.
 35. The thermoplastic article of claim 31 wherein theabrasion resistant coating is a heat-cured silicone, polyurethane orfluorinated polyurethane or an ultraviolet- or electron beam-curedmaterial selected from modified acrylates containing polyurethane,fluorinated polyurethane, silicone, epoxy, polyester, potyether orcaprolactone residues.